EP2155754B1 - Method for the production of dianhydrohexitol diesters - Google Patents
Method for the production of dianhydrohexitol diesters Download PDFInfo
- Publication number
- EP2155754B1 EP2155754B1 EP08736494A EP08736494A EP2155754B1 EP 2155754 B1 EP2155754 B1 EP 2155754B1 EP 08736494 A EP08736494 A EP 08736494A EP 08736494 A EP08736494 A EP 08736494A EP 2155754 B1 EP2155754 B1 EP 2155754B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- isosorbide
- acid
- process according
- ethylhexanoic acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Not-in-force
Links
- 238000000034 method Methods 0.000 title claims description 27
- 150000005690 diesters Chemical class 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229960002479 isosorbide Drugs 0.000 claims description 32
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 claims description 28
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 13
- 238000005886 esterification reaction Methods 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- -1 d) Filtration Chemical compound 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000010626 work up procedure Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000004800 polyvinyl chloride Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920000915 polyvinyl chloride Polymers 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 241001550224 Apha Species 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229920001944 Plastisol Polymers 0.000 description 6
- 239000004999 plastisol Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
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- 238000004817 gas chromatography Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical compound OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- KLDXJTOLSGUMSJ-UNTFVMJOSA-N (3s,3ar,6s,6ar)-2,3,3a,5,6,6a-hexahydrofuro[3,2-b]furan-3,6-diol Chemical compound O[C@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-UNTFVMJOSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 235000014755 Eruca sativa Nutrition 0.000 description 1
- 244000024675 Eruca sativa Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
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- 229920000098 polyolefin Polymers 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
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- 239000000565 sealant Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Definitions
- the present invention relates to a process for the preparation of isosorbide di-2-ethylhexanoate by esterification of isoidide with 2-ethylhexanoic acid in the presence of a catalyst.
- Dianhydrohexitol diesters can be prepared by reacting hexitols, monoanhydrohexitols or preferably dianhydrohexitols with carboxylic acids in the presence of an acidic catalyst with elimination of water, for example in US Pat GB 613 444 . US 3 454 603 or WO 99/045060 described. In WO 01/83488 a method is presented which does not use a homogeneously dissolved catalyst, but a solid acidic ion exchange resin as a catalyst, which facilitates the workup.
- the described methods have the disadvantage that they are unsatisfactory in at least one of the criteria, namely diester selectivity, reaction time or discoloration.
- WO 2006/203338 describes a process for the preparation of Dianhydrohexitoldiestern, which by using a combination of two catalysts, namely an acidic catalyst described therein and hypophosphorous acid (H 3 PO 2 ), the desired diesters in selectivities greater than 95% and low color numbers, expressed by the Yellowness Index, providing.
- a combination of two catalysts namely an acidic catalyst described therein and hypophosphorous acid (H 3 PO 2 )
- H 3 PO 2 hypophosphorous acid
- the isosorbide may be prepared prior to use in the process according to the invention by any known per se method for dehydration of a hexitol or hexitol mixture, followed by the neutralization usually followed by at least one purification of the resulting reaction product.
- the purification step may consist of a simple distillation of the medium resulting from the dehydration. This gives the Dianhydrohexitol compound in the form of a crude distillate, as isosorbide crude distillate.
- This distillate may undergo at least one further purification step, in particular a purification by crystallization in an aqueous phase or in a solvent phase, by concentration in vacuo and / or by a single or multiple treatment with ion exchange resin and / or activated carbon in powder and / or granular form, such as in WO 01/94352 described.
- a further purification step in particular a purification by crystallization in an aqueous phase or in a solvent phase, by concentration in vacuo and / or by a single or multiple treatment with ion exchange resin and / or activated carbon in powder and / or granular form, such as in WO 01/94352 described.
- the starting material used as raw material in the process according to the invention advantageously has a high dianhydrohexitol content of at least 95% by mass, preferably at least 98% by mass and more preferably at least 98.5 mass%, these percentages being based on the total dry weight of the dianhydrohexitol in relation to the dry weight of the starting product.
- Isosorbide or a product which has at least 95% by mass of isosorbide is esterified with 2-ethylhexanoic acid in the presence of hypophosphorous acid in the process according to the invention.
- the 2-ethylhexanoic acid used to form the ester is preferably used in excess, preferably with a molar excess of 5 to 50%, in particular 10 to 30% of the molar amount necessary for the formation of the diester.
- the 2-ethylhexanoic acid thus serves as an entraining agent.
- the distillation of water of reaction and optionally entrainer can also be carried out as a vacuum distillation at a correspondingly reduced pressure.
- another entrainer for example toluene, benzene, cyclohexane, hexane, heptane or xylenes can be used. This may be particularly advantageous if, for example, the vacuum is not adjustable so that the water of reaction distilled off sufficiently quickly as a mixture with the 2-ethylhexanoic acid.
- the reaction water formed in the esterification can also be separated by passing an inert gas through it.
- the conditions to be set for the effective separation of the water of reaction with respect to pressure and inert gas stream are familiar to the expert and can be easily determined by preliminary experiments.
- the obtained by workup of the distillate 2-ethylhexanoic acid can be partially or completely recycled to the reaction. It is also possible to carry out the work-up of the distillate at a later time and to replace all or part of the removed liquid amount with fresh 2-ethylhexanoic acid, ie from a storage vessel.
- the hypophosphorous acid exclusively and exclusively to be used in the process according to the invention for preparing isosorbide di-2-ethylhexanoate by acid-catalyzed esterification of isosorbide as an acidic catalyst is preferably used in the form of an aqueous solution.
- the hypophosphorous acid can be used in any dilutions. Particular preference is given to concentrations of 30 to 60% by mass, in particular 40 to 50% by mass.
- 0.01 to 5% of hypophosphorous acid (calculated as pure substance), preferably 0.03 to 1%, particularly preferably 0.05 to 0.5%, are used.
- the catalyst can be added before or during the esterification, preferably already during heating.
- the esterification temperature can be from 100 to 260.degree. C., preferably from 150 to 260.degree. As a rule, one works under conditions in which the mixture of water and 2-ethylhexanoic acid boils.
- the crude ester mixtures which, in addition to the ester product, also contain certain amounts of the starting product isosorbide, 2-ethylhexanoic acid, catalyst and / or their secondary products and optionally by-products, can be worked up by processes known per se.
- the workup preferably comprises the following steps: separation of the excess 2-ethylhexanoic acid and optionally low boilers by distillation, optionally in the presence of activated carbon, neutralization of the acids present, optionally steam distillation, washing of the crude product, and drying and
- the determination of the color numbers during the reaction or during the workup steps is carried out according to a known procedure with a commercially available color number meter.
- esters of the isosorbide prepared according to the invention are distinguished by particularly high purity and little discoloration and exhibit extremely low color index values.
- the hypophosphorous acid used as esterification catalyst can be separated virtually residue-free.
- the analytically detectable residual phosphorus content is in the ppm order.
- the inventively prepared esters of isosorbide, in paints, inks or paints, in plastisols, adhesives or adhesive components, in sealants, as plasticizers in plastics or plastic components, as a solvent, as a lubricating oil component, as a cooling fluid or drilling fluid or component thereof or as an aid in the Metal processing can be used.
- Preferred plastisols are in particular PVC or PAMA plastisols.
- plastics are polyvinyl chloride (PVC), polyvinyl butyral (PVB), homopolymers and copolymers based on ethylene, propylene, butadiene, vinyl acetate, cellulose acetate, glycidyl acrylate, glycidyl methacrylate, methacrylates, acrylates, acrylates having branched or branched alkyl radicals attached to the oxygen atom of the ester group unbranched alcohols having one to ten carbon atoms, styrene, acrylonitrile, homo- or copolymers of cyclic olefins.
- PVC polyvinyl chloride
- PVB polyvinyl butyral
- homopolymers and copolymers based on ethylene, propylene, butadiene vinyl acetate, cellulose acetate, glycidyl acrylate, glycidyl methacrylate, methacrylates, acrylates, acrylates having
- Examples of representatives of the above groups include the following plastics: polyacrylates having identical or different alkyl radicals having 4 to 8 C atoms, bonded to the oxygen atom of the ester group, in particular with n-butyl, n-hexyl, n-octyl and 2 Ethylhexyl radical, polymethacrylate, polymethylmethacrylate, methylacrylate-butylacrylate copolymers, methylmethacrylate-butylmethacrylate copolymers or generally polyalkylmethacrylates (PAMA), ethylene-vinylacetate copolymers, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene-styrene copolymers, ethylene-propylene copolymers, ethylene-propylene Diene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene rubber, styrene-butadiene
- the products according to the invention for Modification of plastic mixtures for example, the mixture of a polyolefin with a polyamide used.
- compositions of plastic / -en, in particular PVC or PAMA containing the products according to the invention may be included, for example in the following products: Housing for electrical appliances, such as kitchen appliances, computer cases, housings and components of phono and television sets, piping, apparatus, Cables, wire sheathings, insulating tapes, in interior fittings, in vehicle and furniture construction, plastisols, in floor coverings, medical articles, food packaging, gaskets, films, composite films, vinyl records, artificial leather, toys, packaging containers, adhesive tape, clothing, coatings, flocking and printing, fibers for fabrics, coated fabrics.
- electrical appliances such as kitchen appliances, computer cases, housings and components of phono and television sets
- piping, apparatus Cables, wire sheathings, insulating tapes, in interior fittings, in vehicle and furniture construction, plastisols, in floor coverings, medical articles, food packaging, gaskets, films, composite films, vinyl records, artificial leather, toys, packaging containers, adhesive tape, clothing, coatings, flocking and printing
- compositions of plastic, in particular PVC, containing the products according to the invention can be used for example for the production of the following products: piping, hoses, cables, DrahtUmmantelieux, insulating tapes, in vehicle and furniture, plastisols, profiles, floor coverings, medical items (such B. blood bags, tubes, infusion bags, etc.), toys, food packaging, gaskets, films, composite films, plates, artificial leather, wallpaper, packaging containers, adhesive tape, clothing, coatings or fibers for fabrics, shoes, underbody protection, seams, roofing membranes, modeling or balls.
- PVC compositions or plastisols containing PVC and products prepared according to the invention preferably contain from 5 to 250 parts by mass, preferably from 10 to 200 parts by mass and more preferably from 20 to 100 parts by mass of the products of the invention per 100 parts by mass of PVC.
- the batch was then cooled to 80 ° C and neutralized with 50 ml of a 3% NaOH solution. Subsequently, a further 80 ml of a 5% NaCl solution were added and stirred at 90 ° C for a further 30 minutes. The organic phase was then separated and stirred again with 80 ml of 5% NaCl solution for 30 minutes at 90 ° C and the aqueous phase drained again. It was then dried at 125 ° C under vacuum (2 hPa). Then the mixture was stirred again with 2 mass% activated carbon and then filtered (3rd color number measurement). The content of isosorbide diester, determined by GC was 99%.
- the color numbers, determined with the LICO 400 color-coded measuring device are listed in Table 1 following Example 2.
- a sample of about 20 ml was taken from the reaction mixture using a pipette, filtered using a syringe filter and filled into the measuring cuvette of the color number measuring device.
- the device was with calibrated in demineralized water. In each case the color number according to Hazen (APHA) and the iodine color number were measured.
- the hydrogen peroxide / water was distilled off (125 ° C, 5 hPa) (2nd color number measurement).
- the batch was cooled to 80 ° C and neutralized with 35 ml of a 3% NaOH solution.
- a further 40 ml of a 5% NaCl solution were added and stirred at 90 ° C for a further 30 minutes.
- the organic phase was then separated and stirred again with 40 ml of a 5% NaCl solution for 30 minutes at 90 ° C and then drained the aqueous phase. It was then dried at 125 ° C under vacuum (2 hPa).
- the contents of the quartz vessels are transferred to a 25 ml volumetric flask with demineralized water and filled.
- the subsequent measurement on phosphorus is carried out according to DIN EN ISO 11885 on the ICP - OES spectrometer at the wavelengths 177.440 nm and 214.914 nm.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von Isosorbid-di-2-ethylhexanoat durch Veresterung von Isoidid mit 2-Ethylhexansäure in Gegenwart eines Katalysators.The present invention relates to a process for the preparation of isosorbide di-2-ethylhexanoate by esterification of isoidide with 2-ethylhexanoic acid in the presence of a catalyst.
Diester von Dianhydrohexitolen, insbesondere jene auf Basis von Isosorbid, wurden bereits verschiedentlich als geeignete Weichmacher für PVC beschrieben. Nicht zuletzt daher hat es nicht an Versuchen gefehlt, Verfahren zur Herstellung dieser Verbindungen zu entwickeln, die die gewünschten Produkte in hoher Reinheit und mit der für die Verwendung in transparenten Anwendungen unabdingbaren geringen Farbzahl, also möglichst wasserklar, liefern können.Diesters of dianhydrohexitols, especially those based on isosorbide, have been variously described as suitable plasticizers for PVC. Not least, therefore, there has been no lack of attempts to develop processes for the preparation of these compounds, which can deliver the desired products in high purity and with the indispensable for use in transparent applications low color number, so water clear as possible.
Dianhydrohexitoldiester können durch Umsetzung von Hexitolen, Monoanhydrohexitolen oder bevorzugt Dianhydrohexitolen mit Carbonsäuren in Gegenwart eines sauren Katalysators unter Wasserabspaltung hergestellt werden, wie beispielsweise in
Die beschriebenen Verfahren haben jedoch den Nachteil, dass sie zumindest in einem der Kriterien, nämlich Selektivität hinsichtlich des Diesters, Reaktionszeit oder Verfärbung nicht zufriedenstellend sind.However, the described methods have the disadvantage that they are unsatisfactory in at least one of the criteria, namely diester selectivity, reaction time or discoloration.
In
Allerdings zeigt dieses Verfahren den Mangel, dass nur durch eine Kombination zweier Katalysatoren der gewünschte Effekt bezüglich hoher Reinheit und geringer Verfärbung erzielt werden kann. Auch aus Kostengründen wäre ein Verfahren, das mit nur einem Katalysator durchgeführt werden kann und trotzdem die oben genannten Kriterien erfüllt, erstrebenswert. Darüber hinaus wäre es wünschenswert, Produkte mit noch geringerer Farbzahl zu erhalten.However, this method shows the defect that only by a combination of two catalysts the desired effect with respect to high purity and low discoloration can be achieved. Also for cost reasons, a process that can be carried out with only one catalyst and still meets the above criteria would be desirable. In addition, it would be desirable to obtain products with even lower color number.
Völlig überraschend wurde gefunden, dass die Veresterung von Isosorbid mit 2-Ethylhexansäure in Gegenwart von H3PO2 als alleinigem Katalysator mindestens gleichwertige Resultate liefert wie die in
Gegenstand der vorliegenden Erfindung ist daher ein Verfahren zur Herstellung von Isosorbid-di-2-ethylhexanoat umfassend die Verfahrensschritte:
- a) Veresterung von Isosorbid mit 2-Ethylhexansäure mittels saurem Katalysator,
- b) Abdestillieren der überschüssigen 2-Ethylhexansäure,
- c) Reduzierung der Säurezahl mittels basischem Aluminiumoxids,
- d) Filtration,
- a) esterification of isosorbide with 2-ethylhexanoic acid by means of acid catalyst,
- b) distilling off the excess 2-ethylhexanoic acid,
- c) reduction of the acid number by means of basic alumina,
- d) filtration,
Das Isosorbid kann vor dem Einsatz in dem erfindungsgemäßen Verfahren durch jedes an sich bekannte Verfahren zur Dehydratisierung eines Hexitols oder Hexitol-Gemischs hergestellt worden sein, an das sich nach der Neutralisation üblicherweise zumindest eine Aufreinigung des entstandenen Reaktionsprodukts anschließt.The isosorbide may be prepared prior to use in the process according to the invention by any known per se method for dehydration of a hexitol or hexitol mixture, followed by the neutralization usually followed by at least one purification of the resulting reaction product.
Die Aufreinigungsstufe kann aus einer einfachen Destillation des aus der Dehydratisierung hervorgegangenen Mediums bestehen. Dabei erhält man die Dianhydrohexitol-Verbindung in Form eines Rohdestillats, als Isosorbid-Rohdestillat.The purification step may consist of a simple distillation of the medium resulting from the dehydration. This gives the Dianhydrohexitol compound in the form of a crude distillate, as isosorbide crude distillate.
Dieses Destillat kann zumindest eine weitere Aufreinigungsstufe durchlaufen, insbesondere eine Aufreinigung durch Kristallisation in einer wässerigen Phase oder in einer Lösemittelphase, durch Aufkonzentrierung im Vakuum und/oder durch eine ein- oder mehrfache Behandlung mit lonentauscherharz und/oder Aktivkohle in Pulver- und/oder Granulatform, wie etwa in
Unabhängig davon, ob nach der Destillation eine Aufreinigung erfolgt oder nicht, weist das als Rohstoff bei dem Verfahren gemäß der Erfindung verwendete Ausgangsprodukt vorteilhafterweise einen hohen Dianhydrohexitol-Anteil von mindestens 95 Massen-%, vorzugsweise von mindestens 98 Massen-% und besonders bevorzugt von mindestens 98,5 Massen-% auf, wobei sich diese Prozentangaben auf das gesamte Trockengewicht des Dianhydrohexitols im Verhältnis zum Trockengewicht des Ausgangsprodukts beziehen.Irrespective of whether or not it is purified after distillation, the starting material used as raw material in the process according to the invention advantageously has a high dianhydrohexitol content of at least 95% by mass, preferably at least 98% by mass and more preferably at least 98.5 mass%, these percentages being based on the total dry weight of the dianhydrohexitol in relation to the dry weight of the starting product.
In dem erfindungsgemäßen Verfahren wird Isosorbid oder ein Produkt, welches mindestens 95 Massen-% Isosorbid aufweist, mit 2-Ethylhexansäure in Gegenwart von Hypophosphoriger Säure verestert. Die zur Bildung des Esters eingesetzte 2-Ethylhexansäure wird vorzugsweise im Überschuss, bevorzugt mit einem molaren Überschuss von 5 bis 50 %, insbesondere 10 bis 30 % der zur Bildung des Diesters notwendigen molaren Menge eingesetzt.
Zur Entfernung des bei der Veresterung entstehenden Reaktionswassers kann es vorteilhaft sein, wenn dieses mit der 2-Ethylhexansäure aus dem Reaktionsgemisch abdestilliert wird. Die 2-Ethylhexansäure dient somit als Schleppmittel.
Die Abdestillation von Reaktionswasser und gegebenenfalls Schleppmittel kann auch als Vakuumdestillation bei entsprechend reduziertem Druck durchgeführt werden. Optional kann auch ein anderes Schleppmittel, beispielsweise Toluol, Benzol, Cyclohexan, Hexan, Heptan oder Xylole eingesetzt werden. Dies kann insbesondere dann vorteilhaft sein, wenn beispielsweise das Vakuum nicht so einstellbar ist, dass das Reaktionswasser als Gemisch mit der 2-Ethylhexansäure ausreichend schnell abdestilliert.
Alternativ zu oder in Kombination zu dem reduzierten Druck, kann das bei der Veresterung entstehende Reaktionswasser auch durch Durchleiten eines inerten Gases abgetrennt werden.Isosorbide or a product which has at least 95% by mass of isosorbide is esterified with 2-ethylhexanoic acid in the presence of hypophosphorous acid in the process according to the invention. The 2-ethylhexanoic acid used to form the ester is preferably used in excess, preferably with a molar excess of 5 to 50%, in particular 10 to 30% of the molar amount necessary for the formation of the diester.
To remove the water of reaction formed in the esterification, it may be advantageous if it is distilled off with the 2-ethylhexanoic acid from the reaction mixture. The 2-ethylhexanoic acid thus serves as an entraining agent.
The distillation of water of reaction and optionally entrainer can also be carried out as a vacuum distillation at a correspondingly reduced pressure. Optionally, another entrainer, for example toluene, benzene, cyclohexane, hexane, heptane or xylenes can be used. This may be particularly advantageous if, for example, the vacuum is not adjustable so that the water of reaction distilled off sufficiently quickly as a mixture with the 2-ethylhexanoic acid.
As an alternative to or in combination with the reduced pressure, the reaction water formed in the esterification can also be separated by passing an inert gas through it.
Die zur effektiven Abtrennung des Reaktionswassers einzustellenden Bedingungen bezüglich Druck und Inertgasstrom sind dem Fachmann geläufig und können leicht durch Vorversuche ermittelt werden.
Die durch Aufarbeitung des Destillats gewonnene 2-Ethylhexansäure kann teilweise oder vollständig in die Reaktion zurückgeführt werden. Es ist auch möglich, die Aufarbeitung des Destillats zu einem späteren Zeitpunkt durchzuführen und die entfernte Flüssigkeitsmenge ganz oder teilweise durch frische 2-Ethylhexansäure, d. h. aus einem Vorratsgefäß, zu ersetzen.The conditions to be set for the effective separation of the water of reaction with respect to pressure and inert gas stream are familiar to the expert and can be easily determined by preliminary experiments.
The obtained by workup of the distillate 2-ethylhexanoic acid can be partially or completely recycled to the reaction. It is also possible to carry out the work-up of the distillate at a later time and to replace all or part of the removed liquid amount with fresh 2-ethylhexanoic acid, ie from a storage vessel.
Die in dem erfindungsgemäßen Verfahren zur Herstellung von Isosorbid-di-2-ethylhexanoat durch sauer katalysierte Veresterung von Isosorbid als saurer Katalysator ausschließlich und einzig einzusetzende hypophosphorige Säure wird bevorzugt in Form einer wässrigen Lösung angewendet. Die hypophosphorige Säure kann dabei in beliebigen Verdünnungen eingesetzt werden. Besonders bevorzugt sind Konzentrationen von 30 bis 60 Massen-%, insbesondere 40 bis 50 Massen-%. Bezogen auf die Einwaage an Dianhydrohexitol werden 0,01 bis 5 % Hypophosphorige Säure (gerechnet als Reinstoff), bevorzugt 0,03 bis 1 %, besonders bevorzugt 0,05 bis 0,5 % verwendet. Der Katalysator kann vor oder während der Veresterung zugesetzt werden, vorzugsweise bereits beim Aufheizen.The hypophosphorous acid exclusively and exclusively to be used in the process according to the invention for preparing isosorbide di-2-ethylhexanoate by acid-catalyzed esterification of isosorbide as an acidic catalyst is preferably used in the form of an aqueous solution. The hypophosphorous acid can be used in any dilutions. Particular preference is given to concentrations of 30 to 60% by mass, in particular 40 to 50% by mass. Based on the weight of dianhydrohexitol, 0.01 to 5% of hypophosphorous acid (calculated as pure substance), preferably 0.03 to 1%, particularly preferably 0.05 to 0.5%, are used. The catalyst can be added before or during the esterification, preferably already during heating.
Die Veresterungstemperatur kann in Abhängigkeit von der verwendeten Säure oder der Empfindlichkeit der Diester 100 bis 260 °C, bevorzugt 150 bis 260 °C betragen. In der Regel arbeitet man bei Bedingungen, bei denen das Gemisch aus Wasser und 2-Ethylhexansäure siedet.Depending on the acid used or the sensitivity of the diesters, the esterification temperature can be from 100 to 260.degree. C., preferably from 150 to 260.degree. As a rule, one works under conditions in which the mixture of water and 2-ethylhexanoic acid boils.
Die Rohestergemische, die neben dem Esterprodukt noch gewisse Mengen an den Ausgangsproduktenlsosorbid, 2-Ethylhexansäure, Katalysator und/oder deren Folgeprodukte sowie gegebenenfalls Nebenprodukte enthalten, können nach an sich bekannten Verfahren aufgearbeitet werden. Die Aufarbeitung umfasst dabei vorzugsweise folgende Schritte: Abtrennung der überschüssigen 2-Ethylhexansäure und gegebenenfalls Leichtsieder durch Destillation, gegebenenfalls in Anwesenheit von Aktivkohle, Neutralisation der vorhandenen Säuren, optional eine Wasserdampfdestillation, Waschen des Rohproduktes, und Trocknung sowieThe crude ester mixtures which, in addition to the ester product, also contain certain amounts of the starting product isosorbide, 2-ethylhexanoic acid, catalyst and / or their secondary products and optionally by-products, can be worked up by processes known per se. The workup preferably comprises the following steps: separation of the excess 2-ethylhexanoic acid and optionally low boilers by distillation, optionally in the presence of activated carbon, neutralization of the acids present, optionally steam distillation, washing of the crude product, and drying and
Abtrennung restlicher Feststoffe mittels Filtration.
Im Regelfall sind Maßnahmen zur Farbverbesserung nötig, wie zum Beispiel Rühren mit Aktivkohle, Entfärben durch Einsatz von polymeren Adsorbentien oder auch Bleichen mit beispielsweise Wasserstoffperoxid-Lösung. Dabei können je nach angewendetem Aufarbeitungsverfahren die Reihenfolge dieser Schritte verschieden sein. Die vorgenannte Neutralisation kann auch stufenweise durchgeführt werden, indem zunächst mit einer schwachen Base (zum Beispiel Natriumcarbonat- oder Natriumhydrogencarbonat-Lösung) die stärkere Säure H3PO2 und erst im Anschluss an das Abdestillieren noch verbliebene Reste der Carbonsäure durch Neutralisation mit Natronlauge oder Kalilauge oder anderen starken basischen Lösungen entfernt werden.
Es hat sich gezeigt, dass es im Hinblick auf eine Farbverbesserung vorteilhaft ist, einen Waschschritt durchzuführen, bei dem wasserlösliche Verunreinigungen extrahiert und über eine anschließende Phasentrennung entfernt werden. Ohne einen solchen Schritt besteht die Möglichkeit, dass sich bei der zur Trocknung nötigen erhöhten Temperatur der Ansatz wieder verfärbt.
In einer besonders bevorzugten Ausführungsform des Verfahrens kann nach Abdestillieren des Überschusses an 2-Ethylhexansäure eine
Wasserdampfdestillation, bevorzugt in Gegenwart von Aktivkohle, durchgeführt werden, wodurch sowohl der Katalysator als auch die 2-Ethylhexansäure so weit abgetrennt werden können, dass eine Neutralisation und eventuell nachfolgende Waschschritte zur Abtrennung der hierdurch gebildeten Verbindungen unterbleiben können. Wenn die Farb- und Säurezahl des Produktes danach zufrieden stellend ist, kann auf eine weitere Aufarbeitung verzichtet werden. Diese Variante bietet sich besonders dann an, wenn von hochreinen und farblosen Edukten, insbesondere von einer hohen Isosorbid-Qualität ausgegangen wird. In Beispiel 3 wird eine solche Ausführungsform näher beschrieben.Separation of residual solids by filtration.
As a rule, measures for color improvement are necessary, such as stirring with activated carbon, discoloration by using polymeric adsorbents or bleaching with, for example, hydrogen peroxide solution. Depending on the processing method used, the order of these steps may be different. The aforementioned neutralization can also be carried out in stages, by first using a weak base (for example sodium carbonate or sodium bicarbonate solution), the stronger acid H 3 PO 2 and only after distilling off remaining residues of the carboxylic acid by neutralization with sodium hydroxide or potassium hydroxide or other strong basic solutions.
It has been found that, in view of color improvement, it is advantageous to carry out a washing step in which water-soluble impurities are extracted and removed by a subsequent phase separation. Without such a step, there is the possibility that at the elevated temperature required for drying, the approach again discolored.
In a particularly preferred embodiment of the process, after distilling off the excess of 2-ethylhexanoic acid a
Steam distillation, preferably in the presence of activated carbon, are carried out, whereby both the catalyst and the 2-ethylhexanoic acid can be separated so far that neutralization and any subsequent washing steps for the separation of the compounds thus formed can be omitted. If the color and acid number of the product is then satisfactory, can be dispensed with further processing. This variant is particularly suitable when starting from highly pure and colorless starting materials, in particular from a high isosorbide quality. Example 3 describes such an embodiment in more detail.
Die Bestimmung der Farbzahlen während der Reaktion oder während der Aufarbeitungsschritte erfolgt nach an sich bekannter Prozedur mit einem handelsüblichen Farbzahl-Messgerät.The determination of the color numbers during the reaction or during the workup steps is carried out according to a known procedure with a commercially available color number meter.
Die erfindungsgemäß hergestellten Ester des Isosorbids zeichnen sich durch eine besonders hohe Reinheit und geringe Verfärbung aus und zeigen äußerst niedrige Farbzahlwerte. Die als Veresterungskatalysator eingesetzte Hypophosphorige Säure lässt sich praktisch rückstandsfrei abtrennen. Der analytisch nachweisbare Restphosphorgehalt liegt in der ppm-Größenordnung.The esters of the isosorbide prepared according to the invention are distinguished by particularly high purity and little discoloration and exhibit extremely low color index values. The hypophosphorous acid used as esterification catalyst can be separated virtually residue-free. The analytically detectable residual phosphorus content is in the ppm order.
Die erfindungsgemäß hergestellten Ester des Isosorbids, können in Farben, Tinten oder Lacken, in Plastisolen, Klebstoffen oder Klebstoffkomponenten, in Dichtungsmassen, als Weichmacher in Kunststoffen oder Kunststoffkomponenten, als Lösemittel, als Schmierölkomponente, als Kühlflüssigkeit oder Bohrflüssigkeit oder Bestandteil davon oder als Hilfsmittel bei der Metallverarbeitung verwendet werden. Bevorzugte Plastisole sind dabei insbesondere PVC- oder PAMA-Plastisole. Bevorzugte Kunststoffe sind insbesondere Polyvinylchlorid (PVC), Polyvinylbutyral (PVB), Homo- und Copolymere auf Basis von Ethylen, Propylen, Butadien, Vinylacetat, Celluloseacetat, Glycidylacrylat, Glycidylmethacrylat, Methacrylaten, Acrylaten, Acrylaten mit am Sauerstoffatom der Estergruppe gebundenen Alkylresten von verzweigten oder unverzweigten Alkoholen mit einem bis zehn Kohlenstoffatomen, Styrol, Acrylnitril, Homo- oder Copolymere von cyclischen Olefinen.The inventively prepared esters of isosorbide, in paints, inks or paints, in plastisols, adhesives or adhesive components, in sealants, as plasticizers in plastics or plastic components, as a solvent, as a lubricating oil component, as a cooling fluid or drilling fluid or component thereof or as an aid in the Metal processing can be used. Preferred plastisols are in particular PVC or PAMA plastisols. Particularly preferred plastics are polyvinyl chloride (PVC), polyvinyl butyral (PVB), homopolymers and copolymers based on ethylene, propylene, butadiene, vinyl acetate, cellulose acetate, glycidyl acrylate, glycidyl methacrylate, methacrylates, acrylates, acrylates having branched or branched alkyl radicals attached to the oxygen atom of the ester group unbranched alcohols having one to ten carbon atoms, styrene, acrylonitrile, homo- or copolymers of cyclic olefins.
Als Vertreter der obigen Gruppen seien beispielsweise folgende Kunststoffe genannt: Polyacrylate mit gleichen oder verschiedenen Alkylresten mit 4 bis 8 C-Atomen, gebunden am Sauerstoffatom der Estergruppe, insbesondere mit dem n-Butyl-, n-Hexyl-, n-Octyl- und 2-Ethylhexylrest, Polymethacrylat, Polymethylmethacrylat, Methylacrylat-Butylacrylat-Copolymere, Methylmethacrylat-Butylmethacrylat-Copolymere oder allgemein Polyalkylmethacrylate (PAMA), Ethylen-VinylacetatCopolymere, chloriertes Polyethylen, Nitrilkautschuk, Acrylnitril-Butadien-StyrolCopolymere, Ethylen-Propylen-Copolymere, Ethylen-Propylen-Dien-Copolymere, Styrol-Acrylnitril-Copolymere, Acrylnitril-Butadien-Kautschuk, Styrol-Butadien-Elastomere, Methylmethacrylat-Styrol-Butadien-Copolymere, Celluloseacetat, PVB und PVC. Ein besonders bevorzugter Kunststoff ist dabei PVC.Examples of representatives of the above groups include the following plastics: polyacrylates having identical or different alkyl radicals having 4 to 8 C atoms, bonded to the oxygen atom of the ester group, in particular with n-butyl, n-hexyl, n-octyl and 2 Ethylhexyl radical, polymethacrylate, polymethylmethacrylate, methylacrylate-butylacrylate copolymers, methylmethacrylate-butylmethacrylate copolymers or generally polyalkylmethacrylates (PAMA), ethylene-vinylacetate copolymers, chlorinated polyethylene, nitrile rubber, acrylonitrile-butadiene-styrene copolymers, ethylene-propylene copolymers, ethylene-propylene Diene copolymers, styrene-acrylonitrile copolymers, acrylonitrile-butadiene rubber, styrene-butadiene elastomers, methyl methacrylate-styrene-butadiene copolymers, cellulose acetate, PVB and PVC. A particularly preferred plastic is PVC.
Darüber hinaus können die erfindungsgemäß hergestellten Produkte zur Modifizierung von Kunststoffmischungen, beispielsweise der Mischung eines Polyolefins mit einem Polyamid, eingesetzt werden.In addition, the products according to the invention for Modification of plastic mixtures, for example, the mixture of a polyolefin with a polyamide used.
Zusammensetzungen aus Kunststoff/-en, insbesondere PVC oder PAMA, die die erfindungsgemäß hergestellten Produkte enthalten, können beispielsweise in folgenden Produkten enthalten sein: Gehäuse für Elektrogeräte, wie beispielsweise Küchengeräte, Computergehäuse, Gehäuse und Bauteile von Phono- und Fernsehgeräte, Rohrleitungen, Apparate, Kabel, Drahtummantelungen, Isolierbänder, im Innenausbau, im Fahrzeug- und Möbelbau, Plastisole, in Bodenbelägen, medizinische Artikel, Lebensmittelverpackungen, Dichtungen, Folien, Verbundfolien, Schallplatten, Kunstleder, Spielzeug, Verpackungsbehälter, Klebebandfolien, Bekleidung, Beschichtungen, Beflockungen und Bedruckungen, Fasern für Gewebe, beschichtete Gewebe.
Weiterhin können Zusammensetzungen aus Kunststoff, insbesondere PVC, die erfindungsgemäß hergestellte Produkte enthalten, beispielsweise zur Herstellung folgender Erzeugnisse verwendet werden: Rohrleitungen, Schläuche, Kabel, DrahtUmmantelungen, Isolierbänder, im Fahrzeug- und Möbelbau, Plastisole, Profile, Bodenbeläge, medizinische Artikel (wie z. B. Blutbeutel, Schläuche, Infusionsbeutel etc.), Spielzeuge, Lebensmittelverpackungen, Dichtungen, Folien, Verbundfolien, Platten, Kunstleder, Tapeten, Verpackungsbehälter, Klebebandfolien, Bekleidung, Beschichtungen oder Fasern für Gewebe, Schuhe, Unterbodenschutz, Nahtabdichtungen, Dachbahnen, Modelliermassen oder Bälle.Compositions of plastic / -en, in particular PVC or PAMA containing the products according to the invention may be included, for example in the following products: Housing for electrical appliances, such as kitchen appliances, computer cases, housings and components of phono and television sets, piping, apparatus, Cables, wire sheathings, insulating tapes, in interior fittings, in vehicle and furniture construction, plastisols, in floor coverings, medical articles, food packaging, gaskets, films, composite films, vinyl records, artificial leather, toys, packaging containers, adhesive tape, clothing, coatings, flocking and printing, fibers for fabrics, coated fabrics.
Furthermore, compositions of plastic, in particular PVC, containing the products according to the invention can be used for example for the production of the following products: piping, hoses, cables, DrahtUmmantelungen, insulating tapes, in vehicle and furniture, plastisols, profiles, floor coverings, medical items (such B. blood bags, tubes, infusion bags, etc.), toys, food packaging, gaskets, films, composite films, plates, artificial leather, wallpaper, packaging containers, adhesive tape, clothing, coatings or fibers for fabrics, shoes, underbody protection, seams, roofing membranes, modeling or balls.
PVC-Zusammensetzungen oder Plastisole, die PVC und erfindungsgemäß hergestellte Produkte enthalten, enthalten vorzugsweise von 5 bis 250 Massenteile, bevorzugt von 10 bis 200 Massenteile und besonders bevorzugt von 20 bis 100 Massenteile an den erfindungsgemäßen Produkten pro 100 Massenteilen PVC.PVC compositions or plastisols containing PVC and products prepared according to the invention preferably contain from 5 to 250 parts by mass, preferably from 10 to 200 parts by mass and more preferably from 20 to 100 parts by mass of the products of the invention per 100 parts by mass of PVC.
Die folgenden Beispiele sollen die Erfindung erläutern, ohne deren Anwendungsbreite einzuschränken, die sich aus der Beschreibung und den Patentansprüchen ergibt.The following examples are intended to illustrate the invention without limiting its scope, which is apparent from the description and the claims.
In einem 1-Liter-Mehrhalskolben mit Rührer, Wasserabscheider, Rückflusskühler, Tropftrichter und Innenthermometer wurden 146 g (1 Mol) Isosorbid (Fa. Cerestar) mit 438 g (3 Mol) 2-Ethylhexansäure (Fa. Sigma Aldrich) und 0,88 g einer 50%igen wässrigen Lösung von Hypophosphoriger Säure (Fa. Sigma Aldrich) (0,3 Massen-% H3PO2 bezogen auf Isosorbid) unter Rühren auf 240 °C erhitzt. Durch Anlegen eines leichten Vakuums wurde bei dieser Temperatur gewährleistet, dass das Reaktionswasser über den Wasserabscheider komplett ausgetragen werden konnte. Der Reaktionsverlauf wurde über GC-Analytik verfolgt. 7 Stunden nach Siedebeginn war die Reaktion beendet (1. Farbzahlmessung) und der Wasserabscheider wurde durch eine Destillationsbrücke ersetzt, über die bei einer Temperatur bis 200 °C die überschüssige 2-Ethylhexansäure abdestilliert werden konnte. Hierbei wurde sukzessive der Druck bis etwa 2 hPa reduziert. Anschließend wurde der Ansatz auf 90 °C abgekühlt und mit 8,55g (2,5 Massen-% bezogen auf Kolbeninhalt) Wasserstoffperoxid-Lösung (35%ig, Fa. Merck) versetzt und eine Stunde bei konstanter Temperatur gerührt. Anschließend wurde das überschüssige Wasserstoffperoxid und Wasser abdestilliert (125 °C, 5 hPa) (2. Farbzahlmessung). Der Ansatz wurde danach auf 80 °C abgekühlt und mit 50 ml einer 3%igen NaOH-Lösung neutralisiert. Anschließend wurden weitere 80 ml einer 5%igen NaCl Lösung zugegeben und bei 90 °C noch weitere 30 Minuten gerührt. Die organische Phase wurde dann abgetrennt und nochmals mit 80 ml 5%iger NaCl Lösung 30 Minuten bei 90 °C gerührt und die wässrige Phase wiederum abgelassen. Danach wurde bei 125 °C unter Vakuum (2 hPa) getrocknet. Dann wurde der Ansatz nochmals mit 2 Massen-% Aktivkohle gerührt und danach filtriert (3. Farbzahlmessung). Der Gehalt an Isosorbiddiester, ermittelt durch GC lag bei 99 %.146 g (1 mol) of isosorbide (Cerestar Co.) with 438 g (3 mol) of 2-ethylhexanoic acid (Sigma Aldrich) and 0.88 were used in a 1 liter multi-necked flask equipped with stirrer, water separator, reflux condenser, dropping funnel and internal thermometer g of a 50% aqueous solution of hypophosphorous acid (Sigma Aldrich) (0.3 mass% H 3 PO 2 based on isosorbide) with stirring to 240 ° C. By applying a slight vacuum, it was ensured at this temperature that the water of reaction could be completely discharged via the water separator. The course of the reaction was monitored by GC analysis. 7 hours after the start of boiling, the reaction was complete (1st color number measurement) and the water was replaced by a distillation bridge over which at a temperature up to 200 ° C, the excess 2-ethylhexanoic acid could be distilled off. Here, the pressure was successively reduced to about 2 hPa. Subsequently, the batch was cooled to 90 ° C and with 8.55 g (2.5% by mass based on the contents of the flask) of hydrogen peroxide solution (35%, Fa. Merck) and stirred for one hour at a constant temperature. Subsequently, the excess hydrogen peroxide and water were distilled off (125 ° C, 5 hPa) (2nd color number measurement). The batch was then cooled to 80 ° C and neutralized with 50 ml of a 3% NaOH solution. Subsequently, a further 80 ml of a 5% NaCl solution were added and stirred at 90 ° C for a further 30 minutes. The organic phase was then separated and stirred again with 80 ml of 5% NaCl solution for 30 minutes at 90 ° C and the aqueous phase drained again. It was then dried at 125 ° C under vacuum (2 hPa). Then the mixture was stirred again with 2 mass% activated carbon and then filtered (3rd color number measurement). The content of isosorbide diester, determined by GC was 99%.
Die Farbzahlen, ermittelt mit dem Farbzahl-Messgerät LICO 400 (Firma Hach-Lange, 11 mm Rundküvette), sind im Anschluss an Beispiel 2 in Tabelle 1 aufgeführt. Dazu wurde dem Reaktionsansatz mit einer Pipette eine Probe von ca. 20 ml entnommen, mit Hilfe eines Spritzenfilters filtriert und in die Messküvette des Farbzahl-Messgerätes gefüllt. Vor Aufnahme der Messungen wurde das Gerät mit vollentsalztem Wasser kalibriert. Gemessen wurden jeweils die Farbzahl nach Hazen (APHA) und die lod-Farbzahl.The color numbers, determined with the LICO 400 color-coded measuring device (Hach-Lange, 11 mm round cuvette), are listed in Table 1 following Example 2. For this purpose, a sample of about 20 ml was taken from the reaction mixture using a pipette, filtered using a syringe filter and filled into the measuring cuvette of the color number measuring device. Before taking the measurements, the device was with calibrated in demineralized water. In each case the color number according to Hazen (APHA) and the iodine color number were measured.
In Anlehnung an Beispiel 2, Versuch 6 aus
In einem 4-Liter-Destillationskolben mit Rührstäbchen, Wasserabscheider, Rückflusskühler, Tropftrichter und Innenthermometer wurden 876 g (6 Mol) Isosorbid (Polysorb P, Fa. Roquette Frères) mit 2190 g (15 Mol) 2-Ethylhexansäure (Fa. Sigma Aldrich) und 1,75 g einer 50%igen wässrigen Lösung von Hypophosphoriger Säure (Fa. Sigma Aldrich) (0,2 Massen-% H3PO2 bezogen auf Isosorbid) unter Rühren auf 240 °C erhitzt. Durch Anlegen eines leichten Vakuums wurde bei dieser Temperatur gewährleistet, dass das Reaktionswasser über den Wasserabscheider komplett ausgetragen werden konnte. Der Reaktionsverlauf wurde über GC-Analytik verfolgt. 12,5 Stunden nach Siedebeginn war die Reaktion beendet (Hazen-Farbzahl in 50mm Küvette nach Abkühlen APHA = 41). Von diesem Ansatz wurden 750 g entnommen, in eine entsprechend kleinere Apparatur, bei der der Wasserabscheider durch eine Destillationsbrücke ersetzt war, gegeben und mit 1 Massen-% Aktiv-Kohle vom Typ A-Supra EUR (Fa. Norit) versetzt und auf ein Vakuum von 27 hPa eingestellt. Unter Rühren wurde bis zu bei einer Temperatur von 240 °C die überschüssige 2-Ethylhexansäure abdestilliert. Anschließend wurde die Heizung ausgeschaltet und der Ansatz durch tropfenweise Zugabe von 40 g Wasser über den Tropftrichter bei einem Druck von 27 bis 33 hPa auf 140 °C abgekühlt, wodurch eine weitere Reinigung des Ansatzes (Prinzip Wasserdampfdestillation) erfolgte. Danach wurde mittels Filtration das Produkt von der Aktivkohle abgetrennt und eine Probe entnommen (Farbzahl nach DIN ISO 6271: APHA 13, Säurezahl nach DIN EN ISO 2114 0,11 mg KOH/g). Zur weiteren Reduzierung der Säurezahl wurde mit 2 % basischem Aluminiumoxid (Fa. Sigma Aldrich) noch eine Stunde bei einer Temperatur von 100 °C gerührt.
Nach Filtration zeigte das Produkt folgende Werte:
- Säurezahl nach DIN EN ISO 2114: 0,008 mg KOH/g
- Farbzahl nach DIN ISO 6271: APHA = 8
- Gehalt an P: < 10 ppm
After filtration the product showed the following values:
- Acid number according to DIN EN ISO 2114: 0.008 mg KOH / g
- Color number according to DIN ISO 6271: APHA = 8
- Content of P: <10 ppm
Gehalt an P, bestimmt mittels Mikrowellenaufschluss der organischen Matrix zur Elementbestimmung mittels ICP-OES nach DIN EN ISO 11885:
- Die Bestimmung der P-Konzentration erfolgt in wässriger, salpetersaurer Lösung. Die organische Matrix wird mittels Mikrowellenaufschluss unter Druck mit Salpetersäure zerstört.
- Gerät: Mikrowelle Ultra Clave III, Firma MLS
- Reagenzien: Salpetersäure, 65%ig; VE-Wasser
- The P concentration is determined in aqueous, nitric acid solution. The organic matrix is destroyed by microwave digestion under pressure with nitric acid.
- Device: Microwave Ultra Clave III, company MLS
- Reagents: nitric acid, 65%; VE water
Durchführung:
0,4g werden auf der Analysenwaage in ein 15 ml Quarzgefäß eingewogen und mit 6 ml Salpetersäure und 3 ml VE-Wasser versetzt. Nach Einbau in den Autoklaven der Mikrowelle erfolgt der Aufschluss automatisch nach Druck- und Temperaturkontrolle.
0.4 g are weighed on the analytical balance in a 15 ml quartz flask and mixed with 6 ml of nitric acid and 3 ml of deionized water. After installation in the autoclave of the microwave, the digestion is carried out automatically after pressure and temperature control.
Nach erfolgtem Aufschluss wird der Inhalt der Quarzgefäße auf einen 25 ml Messkolben mit VE-Wasser überführt und aufgefüllt. Die anschließende Messung auf Phosphor erfolgt nach DIN EN ISO 11885 am ICP - OES Spektrometer bei den Wellenlängen 177,440 nm und 214,914 nm.After digestion, the contents of the quartz vessels are transferred to a 25 ml volumetric flask with demineralized water and filled. The subsequent measurement on phosphorus is carried out according to DIN EN ISO 11885 on the ICP - OES spectrometer at the wavelengths 177.440 nm and 214.914 nm.
Claims (7)
- A process for the preparation of isosorbide di-2-ethylhexanoate comprising the steps of:a) Esterification of isosorbide with 2-ethylhexanoic acid by means of acidic catalyst,b) Distillation to remove the excess 2-ethylhexanoic acid,c) Reduction of the acid number by means of basic aluminium oxide,d) Filtration,
hypophosphorous acid exclusively is used as catalyst in step a). - A process according to claim 1,
characterized in that
the 2-ethylhexanoic acid is used in a molar excess of from 5 to 50%, in particular from 10 to 30%, of the molar amount needed for formation of the diester. - A process according to either of claims 1 and 2,
characterized in that,
based on the starting weight of isosorbide, the amount used of hypophosphorous acid (calculated as pure substance) is from 0.01 to 5%, preferably from 0.03 to 1%, particularly preferably from 0.05 to 0.5%. - A process according to any of claims 1 to 3,
characterized in that
the hypophosphorous acid to be used is used in the form of an aqueous solution, preferably at a concentration of from 30 to 60% by weight, in particular from 40 to 50% by weight. - A process according to any of claims 1 to 4,
characterized in that
during the work-up of the resultant isosorbide diesters a treatment with activated charcoal and/or hydrogen peroxide takes place to improve colour. - A process according to any of claims 1 to 5,
characterized in that
the water of reaction produced during the esterification reaction is removed from the reaction mixture by distillation with the 2-ethylhexanoic acid as entrainer. - A process according to any of claims 1 to 6,
characterized in that
some or all of the 2-ethylhexanoic acid obtained via work-up of the distillate is returned to the reaction.
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DE200710028702 DE102007028702A1 (en) | 2007-06-21 | 2007-06-21 | Process for the preparation of dianhydrohexitol diesters |
PCT/EP2008/054916 WO2008155159A1 (en) | 2007-06-21 | 2008-04-23 | Method for the production of dianhydrohexitol diesters |
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CN (1) | CN101328183B (en) |
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WO2023088773A1 (en) | 2021-11-17 | 2023-05-25 | Evonik Operations Gmbh | Dielectric fluid compositions comprising low viscosity monoesters with improved low temperature performance |
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US20100257657A1 (en) * | 2006-03-01 | 2010-10-14 | Smarthealth, Inc. | Polylactic acid gloves and methods of manufacturing same |
DE102009022445A1 (en) | 2009-05-23 | 2009-12-24 | Clariant International Limited | Liquid composition, useful e.g. to preserve cosmetic, dermatological or pharmaceutical products, preferably e.g. creams, cream gel, lotions, shampoos, shower baths, wet wipes and deodorants, comprises sorbitan monocaprylate and alcohol |
DE102011004677A1 (en) | 2011-02-24 | 2012-08-30 | Evonik Oxeno Gmbh | Heptyl ester of furandicarboxylic acid |
DE102011077857A1 (en) * | 2011-06-21 | 2012-12-27 | Evonik Oxeno Gmbh | Dianhydrohexitol diester of 2-ethylheptanoic acid |
CN103747680B (en) | 2011-08-04 | 2016-01-06 | 克拉里安特国际有限公司 | Comprise the composition of isobide monoesters and isobide diester |
BR112014002594A2 (en) * | 2011-08-04 | 2017-04-11 | Clariant Int Ltd | use of isosorbide diesters as thickeners |
EP2739146B1 (en) | 2011-08-04 | 2015-11-25 | Clariant International Ltd | Use of isosorbide monoesters as fungicidally active substances |
CN103717071B (en) | 2011-08-04 | 2016-01-06 | 克拉里安特国际有限公司 | Comprise the composition of isobide monoesters and N-pyridone ketone |
ES2607654T3 (en) | 2011-08-04 | 2017-04-03 | Clariant International Ltd | Compositions containing isosorbide monoesters and alcohols, which contain at least one aromatic group |
EP2739137B1 (en) | 2011-08-04 | 2017-06-07 | Clariant International Ltd | Use of isosorbide monoesters as thickeners |
DE102011089495A1 (en) | 2011-12-21 | 2013-06-27 | Evonik Industries Ag | Dianhydrohexitol diester mixture GC |
DE102011089493A1 (en) | 2011-12-21 | 2013-06-27 | Evonik Industries Ag | Dianhydrohexitol diester mixture NMR |
FR2990210B1 (en) * | 2012-05-03 | 2014-05-02 | Roquette Freres | PLASTICIZING COMPOSITIONS COMPRISING GELIFICATION ACCELERATORS BASED ON LOW WEIGHT 1.4: 3.6-DIANHYDROHEXITOL ESTER |
AU2014366354A1 (en) * | 2013-12-19 | 2016-06-16 | Archer Daniels Midland Company | An improved glycol acylation process |
US10597402B2 (en) | 2015-03-27 | 2020-03-24 | Sytheon Limited | Compositions and methods for restoring epidermal integrity and function and treating dermatological diseases |
DK3273951T3 (en) | 2015-03-27 | 2020-11-02 | Symbionyx Pharmaceuticals Inc | Compositions and methods for treating psoriasis |
CN108658998B (en) * | 2018-04-28 | 2019-12-03 | 山东岩海建设资源有限公司 | A kind of isobide ester plasticiser and its preparation method and application |
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GB613444A (en) | 1946-01-17 | 1948-11-29 | John George Mackay Bremner | Improvements in and relating to the production of heterocyclic compounds |
US3454603A (en) | 1966-05-18 | 1969-07-08 | Atlas Chem Ind | Method of preparing 1,4-3,6-dianhydroiditol and 1,4-3,6-dianhydroglucitol |
DE19505100A1 (en) * | 1995-02-15 | 1996-08-22 | Basf Ag | Alk (en) yldicarboxylic acid bisesters, their use and processes for their preparation |
AU751753B2 (en) | 1998-03-04 | 2002-08-29 | Ato B.V. | Bicyclooctane derivatives as plasticisers |
NL1015119C2 (en) | 2000-05-04 | 2001-11-06 | Inst Agrotechnologisch Onderzoek Ato Dlo | Improved synthesis of anhydroglycitol esters with improved color. |
FR2810040B1 (en) | 2000-06-09 | 2004-04-09 | Roquette Freres | PROCESS FOR PURIFYING A COMPOSITION CONTAINING AT LEAST ONE PRODUCT OF INTERNAL DEHYDRATION OF A HYDROGENIC SUGAR |
FR2883877B1 (en) | 2005-04-01 | 2008-10-10 | Roquette Freres | PROCESS FOR THE PREPARATION OF DIANHYDROHEXITOL DIESTER (S) COMPOSITIONS |
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WO2023088773A1 (en) | 2021-11-17 | 2023-05-25 | Evonik Operations Gmbh | Dielectric fluid compositions comprising low viscosity monoesters with improved low temperature performance |
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